Jean Pierre Fouassier

Institut de Science des Matériaux de Mulhouse, Mulhousen, Alsace, France

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Publications (306)757.74 Total impact

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    ABSTRACT: A series of naphthalimide derivatives containing tertiary amine groups (DNNDs) have been prepared. Some of these derivatives (e.g. DNND3, DNND4 and DNND5) exhibit interesting shifted absorption so that they can be utilized as versatile photoinitiators upon exposure to various violet and blue LEDs (385, 405, 455 and 470 nm). They are particularly efficient for the cationic photopolymerization of an epoxide and the free radical photopolymerization of an acrylate. The thiol–ene photopolymerization, as well as the synthesis of interpenetrating polymer networks (of epoxide/acrylate blend) IPNs, is feasible. Remarkably, the production of hydrogels can also be easily achieved using a DNND derivative after inclusion in a cyclodextrin cavity. The photochemical mechanisms have been comprehensively investigated by steady state photolysis, Electron Spin Resonance (ESR), fluorescence, electrochemistry and laser flash photolysis and discussed in detail.
    No preview · Article · Dec 2015 · Polymer Chemistry
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    ABSTRACT: A novel photoinitiator based on a spiroxanthene scaffold in the presence of an iodonium salt is proposed for the cationic ring-opening polymerization of a diepoxide, as well as for the free-radical polymerization of an acrylate upon violet LED exposure (385 and 405 nm). Good-to-excellent rates of polymerization and final conversions are obtained. These systems are characterized by a higher reactivity compared with that of anthracene/iodonium salt used as reference for cationic near UV polymerization. The addition of a poly(ionic liquid) improves the cationic polymerization profiles. The photochemical mechanisms are studied by steady-state photolysis, fluorescence, and electron spin resonance spin-trapping techniques. Molecular orbital calculations give an insight into the light absorption properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43213
    No preview · Article · Nov 2015

  • No preview · Article · Nov 2015
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    ABSTRACT: Abstract: (i) 5 to 80 percent by weight based on the total weight of the composition of a polymerizable matrix containing polymerizable monomers; (ii) a polymerization initiator system containing (a) an alpha-diketone photoinitiator compound having a light absorption maximum in the range from 300 to 500 nm; (b) a coinitiator compound of the following formula (I): A-H (I) wherein A is a moiety of the following formula (II) R 1 R2R3X (II) wherein X represents Si, Ge, or Sn and R 1 represents a hydrogen atom, an organic moiety or a different moiety A; R2 and R3 which are independent from each other, represent an organic moiety; and (c) one or more compounds selected from the following group: (I) an iodonium compound of the following formula (III): R -l+-R5 Y (III) wherein R4 and R5 which are independent from each other represent an organic moiety, andy- is an anion; (2) a sulfonium compound ofthe following formula (IV): R6R7R8S+ Y (IV) wherein R6, R7 and R8 which are independent from each other, represent an organic moiety or wherein any two of R 6, R7 and R8 form a cyclic structure together with the sulfur atom to which they are bound, and Yis an anion; (3) a phosphonium compound of the following formula (V): R9R10R11 p+y- (V) wherein R9, R10 and R11 which are independent from each other, represent an organic moiety, andy- is an anion; and (4) a pyridinium salt.
    Full-text · Patent · Oct 2015
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    ABSTRACT: The camphorquinone (CQ)/amine and CQ/diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide (TPO)/amine photoinitiating systems (PISs) are largely used in the area of dental resins, but the role of the light source in connection with the excited state processes has not been deeply investigated so far. Here, a state-of-the-art analysis on the photochemistry of these PISs is provided. Novel experiments using electron spin resonance spin trapping, cyclic voltammetry, photolysis as well as the recording of film polymerization profiles (by real time Fourier transform infrared (FTIR) measurements) of a trifunctional low molecular weight acrylate and a more viscous bisphenol A-glycidyl methacrylate/triethyleneglycol dimethacrylate blend under well-defined irradiation conditions (dental light-emitting diode (LED) and monochromatic laser diode; this has not been done before) are carried out. Although a noticeable improvement under a polychromatic Xe lamp is clearly obtained in the literature when using CQ/TPO/amine compared to CQ/amine, the polymerization profiles of the representative (meth)acrylate monomers are only slightly better under a dental blue LED irradiation (band spectrum centred at 477 nm) and not affected under a laser diode at 473 nm. This work allows a complete and final description of the overall initiation mechanisms in these PISs.
    Full-text · Article · Oct 2015 · Macromolecular Chemistry and Physics
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    ABSTRACT: Dental composition comprising (i) 5 to 80 percent by weight based on the total weight of the composition of a polymerizable matrix containing polymerizable monomers; (ii) a polymerization initiator system containing (a) an alpha-diketone photoinitiator compound having a light absorption maximum in the range from 300 to 500 nm; and (b) a coinitiator compound of the following formula (I): A-H (I) wherein A is a moiety of the following formula (II) R1R2R3X- (II) wherein Xrepresents Si, Ge, or Sn and R1 represents a hydrogen atom, an organic moiety or a different moiety A; R2 and R3 which are independent from each other, represent an organic moiety.
    Full-text · Patent · Sep 2015
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    ABSTRACT: This article reports on the presumably first use of iron complexes (FeC) as potential photocatalysts for controlled radical photopolymerization reactions (CRP2). Three compounds were designed and investigated. Good linear evolutions of the molecular weight (Mn) with the conversion were observed. A comparison was provided with a reference iridium (III) complex [Ir(ppy)3 where ppy stands for 2-phenylpyridine]. The on/off photopolymerization experiments highlight the presence of dormant species and a re-initiation on demand upon irradiation. This unique re-initiation property was used for the modification of surfaces (hydrophilic/hydrophobic properties) and surface patterning as well as the synthesis of a block co-polymer (PMMA-b-PBA). A comparative analysis of the behavior of these iron complexes in thermally and photochemically activated polymerization was provided. The chemical mechanisms were studied by steady state photolysis, laser flash photolysis, cyclic voltammetry, luminescence quenching, and electron spin resonance experiments. A catalytic cycle was proposed with two steps: (i) the oxidation of the FeC excited state by an alkyl halide and (ii) the reduction by the oxidized form (FeC°+) by an amine or the macroradicals leading to the regeneration of the catalyst. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    No preview · Article · Sep 2015 · Journal of Polymer Science Part A Polymer Chemistry
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    ABSTRACT: A carbazole-bound ferrocenium salt [i.e., (η6-Carbazole) (η5-cyclopentadienyl) iron hexafluorophosphate—FS] is proposed as an efficient photoinitiator for the cationic ring-opening polymerization of epoxides under air upon the exposure to a near-UV LED at 385 nm or a visible LED at 405 nm. When using this ferrocenium salt FS (0.2 wt%)/diphenyliodonium hexafluorophosphate or FS (0.2 wt%)/diphenyliodonium hexafluorophosphate/N-vinylcarbazole, final epoxide conversions of 55–66 % can be obtained after 800 s of irradiation at 385 or 405 nm. Reference cationic photoinitiators (i.e., diphenyliodonium hexafluorophosphate; 9-(4-hydroxyethoxyphenyl) thianthrenium hexafluorophosphate and triphenylsulfonium hexafluorophosphate) are unable to initiate the epoxide polymerization under the same conditions. The photochemical mechanisms for the formation of the initiating species are studied using steady-state photolysis, cyclic voltammetry, laser flash photolysis and electron spin resonance spin-trapping techniques. Molecular orbital calculations help to describe the absorption properties and the initiation step. The performance attained when using FS alone is really promising for applications under soft near-UV or visible light-emitting diode irradiation. Graphical abstract
    No preview · Article · Aug 2015 · Polymer Bulletin
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    Full-text · Conference Paper · Aug 2015
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    ABSTRACT: The utilization of visible lights for the fabrication of polymeric materials is recognized as a promising and environmentally friendly approach. This process relies on the photochemical generation of reactive species (e.g., radicals, radical cations, or cations) from well-designed photoinitiators (PIs) or photoinitiating systems (PISs) to initiate the polymerization reactions of different monomers (acrylates, methacrylates, epoxides, and vinyl ethers). In spite of the fact that metal complexes such as ruthenium- or iridium-based complexes have found applications in organic and polymer synthesis, the search of other low-cost metal-based complexes as PISs is emerging and attracting increasing attentions. Particularly, the concept of the photoredox catalysis has appeared recently as a unique tool for polymer synthesis upon soft conditions (use of light emitting diodes and household lamp). This highlight focuses on recently designed copper and iron complexes as PI catalysts in the application of photoinduced polymerizations (radical, cationic, interpenetrated polymer networks, and thiol-ene) or controlled radical polymerization under visible light irradiation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    Full-text · Article · Aug 2015 · Journal of Polymer Science Part A Polymer Chemistry
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    ABSTRACT: Naphthalimide derivatives (NDAs) with amino- or alkylthio-substituents have been synthesized and combined in photoinitiating systems (PIS) with an iodonium salt, N-vinylcarbazole, an amine, or 2,4,6-tris(trichloromethyl)-1,3,5-triazine to produce radicals, cation radicals, or cations. The photochemical mechanisms are investigated by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The generated reactive species are capable of initiating the cationic polymerization (CP) of epoxides under air or the free radical polymerization (FRP) of acrylates in laminate upon exposure to visible lights delivered by a halogen lamp, a cold white light-emitting diode (LED), or LEDs at 385, 395, 405, 455, or 470 nm. Compared to the well-known camphorquinone based systems, the novel NDA containing PISs exhibit higher efficiencies both for CP and FRP. Remarkably, the photo­bleaching of some NDAs is significant, and colorless final polymer coatings are obtained. The structure/photochemical property relationships of NDAs are discussed in detail (redox potentials, fluorescence, rate constants of reactions, etc.) to shed some light on their respective photoinitiating ability.
    No preview · Article · Aug 2015 · Macromolecular Chemistry and Physics
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    ABSTRACT: Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one-component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42759.
    Full-text · Article · Aug 2015 · Journal of Applied Polymer Science
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    ABSTRACT: Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1-ANH8) have been prepared and combined with an iodonium salt (and optionally N-vinylcarbazole) or an amine (and optionally 2,4,6-tris(trichloromethyl)-1,3,5-triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (∼ 12 mW cm−2), laser diode at 405 nm (∼1.5 mW cm−2) or blue LED centered at 455 nm (80 mW cm−2). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well-known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin-trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    No preview · Article · Aug 2015 · Journal of Polymer Science Part A Polymer Chemistry
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    ABSTRACT: Titanium propoxide, titanium isopropoxide, and titanium (triethanolaminato) isopropoxide are proposed as high-performance additives to overcome the oxygen inhibition effects in the free radical photopolymerization of a low-viscosity monomer thin film, under air and upon a low-intensity UV light activation. Indeed, when added to a Type I photoinitiator such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BAPO), noticeably higher conversions are achieved under air (48% vs. 30%). The in situ formation of Ti-based nanoparticles is also observed. The photochemical properties of these types of Ti-based compounds as well as their interaction with BAPO are investigated by steady-state photolysis and electron spin resonance. Molecular orbital calculations give an interesting insight into the possible reactions. A chemical mechanism is also proposed. Photoinitiating systems based on titanium propoxide derivatives are used as additives for avoiding the oxygen inhibition during the photopolymerization of acrylate and the generation of Ti NPs. Higher conversions are achieved under air. The photochemical properties of these types of Ti-based compounds as well as their interaction with BAPO are investigated by steady-state photolysis and electron spin resonance.
    No preview · Article · Jul 2015 · Macromolecular Chemistry and Physics
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    ABSTRACT: Series of diketopyrrolopyrrole derivatives (DPPs) and indigo derivatives (IDGs) are synthesized and applied as photoinitiators (PIs) for the cationic polymerization (CP) of epoxides, the free radical polymerization (FRP) of acrylates or the thiol-ene polymerization under different lights (purple, blue, green, yellow, red LEDs and green laser diode). The photochemical mechanisms involved in the presence of these PIs and additives (iodonium salt (Iod), N-vinylcarbazole (NVK), amine (MDEA) or 2,4,6-tris(trichloromethyl)-1,3,5-triazine (R-Cl)) are investigated by steady state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques. Real-time infrared spectroscopy studies reveal that DPP4/Iod/NVK is very efficient for both CP and FRP and, compared to two references (Eosin-Y and camphorquinone), displays noticeably higher polymerization efficiencies. Panchromatic curable formulations exhibiting an almost constant photosensitivity from the blue to the red are proposed.
    No preview · Article · Jun 2015
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    Jacques Lalevée · Jean‐Pierre Fouassier
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    ABSTRACT: This chapter reviews visible light-induced radical polymerization reactions in the 380-800 nm range. It describes the role of the absorbing species (dye) and the complete multicomponent photoinitiating systems (PISs) (dye and additives). The chapter focuses on the original works of the dye-based PISs that have been proposed over the years. It also focuses on the latest developments and the actual trends of research, in particular the novel perspectives of applications under soft irradiation conditions. Near-field optical techniques (evanescent waves and field enhancement) facilitate the manufacture of nano-objects. The light is confined in a nanometric volume which enables high luminous power densities: even low reactivity PISs can work in these conditions. The dye-based radical PISs described throughout the chapter encounters a large variety of reactions in the radiation curing field, the imaging and laser imaging field or the medical and dentistry fields.
    Full-text · Article · May 2015
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    ABSTRACT: Four novel onium salts (onium-polyoxometalate) have been synthesized and characterized. They contain a diphenyliodonium or a thianthrenium (TH) moiety and a polyoxomolybdate or a polyoxotungstate as new counter anions. Outstandingly, these counter anions are photochemically active and can sensitize the decomposition of the iodonium or TH moiety through an intramolecular electron transfer. The phenyl radicals generated upon UV light irradiation (Xe–Hg lamp) are very efficient to initiate the radical polymerization of acrylates. Cations are also generated for the cationic polymerization of epoxides. Remarkably, these novel iodonium and TH salts are characterized by a higher reactivity compared with that of the diphenyliodonium hexafluorophosphate and the commercial TH salt, respectively. Interpenetrating polymer networks can also be obtained under air through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend (monomer conversions > 65%). The photochemical mechanisms are studied by steady-state photolysis, cyclic voltammetry, and electron spin resonance techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015.
    Full-text · Article · Apr 2015 · Journal of Polymer Science Part A Polymer Chemistry
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    ABSTRACT: Seven naphthalimide derivatives (NDP1-NDP7) with different substituents have been designed as versatile photoinitiators (PIs), and some of them when combined with an iodonium salt (and optionally N-vinylcarbazole) or an amine (and optionally chlorotriazine) are expected to exhibit an enhanced efficiency to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources (i.e., the LED at 385, 395, 405, 455, or 470 nm or the polychromatic visible light from the halogen lamp). Remarkably, some studied naphthalimide derivative based photoinitiating systems (PIS) are even more efficient than the commercial type I photoinitiator bisacylphosphine oxide and the well-known camphorquinone-based systems for cationic or radical photopolymerization. A good efficiency upon a LED projector at 405 nm used in 3D printers is also found: a 3D object can be easily created through an additive process where the final object is constructed by coating down successive layers of material. As another example of their broad potential, a NDP compound enveloped in a cyclodextrin (CD) cavity, leads to a NDP-CD complex which appears as a very efficient water-soluble photoinitiator when combined with methyldiethanol amine to form a hydrogel. The high interest of the present photoinitiator (NDP2) is its very high reactivity, allowing synthesis in water upon LED irradiation as a green way for polymer synthesis.The structure/reactivity/efficiency relationships as well as the photochemical mechanisms associated with the generation of the active species (radicals or cations) are studied by different techniques including steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin-trapping methods.
    Full-text · Article · Apr 2015 · Macromolecules
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    ABSTRACT: Isoquinolinone derivatives bearing amino- or nitro- substituent (IQNs) have been synthesized as photoinitiators and combined with various additives (i.e., iodonium salt, N-vinylcarbazole, amine or 2,4,6-tris(trichloromethyl)−1,3,5-triazine) to initiate ring-opening cationic polymerizations (CP) or free radical polymerizations under exposure to visible LEDs (e.g., LEDs at 405 nm or 455 nm, or cold white LED) or a halogen lamp. Compared to the well-known camphorquinone-based systems, the novel IQNs-based combinations employed here demonstrate higher efficiencies for the CP of epoxides. The photochemically generated reactive species (i.e., cations and radicals) from the IQNs-based systems have been investigated by steady state photolysis, cyclic voltammetry, fluorescence, laser flash photolysis, and electron spin resonance spin trapping techniques. The structure/reactivity/photoinitiating ability relationships of IQNs-based combinations are also discussed; the crucial role of the excited state lifetimes of the photoinitiators to ensure efficient quenching by additives is clearly underlined. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    No preview · Article · Apr 2015 · Journal of Polymer Science Part A Polymer Chemistry
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    ABSTRACT: N,N'-dibutylquinacridone (DBQA) is utilized here for the first time as a high-performance panchromatic photoinitiator for the cationic polymerization (CP) of epoxides, the free radical polymerization (FRP) of acrylates, the thiol-ene polymerization and the synthesis of interpenetrated polymer networks (epoxide/acrylate) under violet, blue, green and yellow lights (emitted from LED at 405 nm, 470 nm, 520 nm, or 594 nm, or laser diode at 532 nm). It confers a panchromatic character to the photopolymerizable matrices. Remarkably, the proposed DBQA based photoinitiating systems exhibit quite excellent efficiency (the final monomer conversion for multifunctional monomers at room temperature can reach 62% and 50% in CP and FRP, respectively) and appear as much more powerful than the camphorquinone or Eosin-Y containing reference systems for visible light. For green light, DBQA is much more reactive than the literature reference (Eosin-Y) and for blue light, a good reactivity is found compared with camphorquinone. The photochemical mechanisms are studied by molecular orbital calculations, steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    No preview · Article · Mar 2015 · Journal of Polymer Science Part A Polymer Chemistry

Publication Stats

5k Citations
757.74 Total Impact Points

Institutions

  • 2014-2015
    • Institut de Science des Matériaux de Mulhouse
      Mulhousen, Alsace, France
    • University of New South Wales
      • School of Chemistry
      Kensington, New South Wales, Australia
  • 1994-2014
    • Université de Haute-Alsace
      • • Institut de Science des Matériaux de Mulhouse : IS2M
      • • Département de Chimie
      Mulhousen, Alsace, France
  • 1986-2013
    • French National Centre for Scientific Research
      Lutetia Parisorum, Île-de-France, France
  • 1997
    • Lamberti SpA
      Albizzate, Lombardy, Italy
  • 1995
    • University of Bologna
      Bolonia, Emilia-Romagna, Italy